Amino-substituted 2-cumaryl-(3)-chromenylium salts

ABSTRACT

The present invention is directed to novel amino-substituted 2-cumaryl-3&#39;-chromenylium salts of the general formula ##STR1## wherein R 3  and R 7  are a dialkyl or cycloalkyl disubstituted amino group, hydrogen, or hydroxy group, provided that at least one of R 3  and R 7  is an amino group, R 1 , R 2 , R 4 , R 5 , R 6 , and R 8  are hydrogen, an alkoxy group, or two of these substituents together form an aromatic ring, provided that R 1 , R 2  and R 4  may be the same or different, and R 5 , R 6  and R 8  may be the same or different, and Y -  is an acidic anion and to the process for their preparation.

BACKGROUND OF THE INVENTION AND PRIOR ART STATEMENT

The invention relates to a process for the preparation of amino-substituted 2-cumaryl-(3')-chromenylium salts. Compounds of this kind are important as dyestuffs, especially in copying processes and, in electrophotography.

According to the state of the art, a method for the preparation of 2-cumaryl-(3')-chromenylium salts is known (DE-OS No. 2,349,960) but it relates only to the preparation of 2-cumaryl-(3')-chromenylium salts which do not possess any amino-functional groups.

Amino-substituted 2-cumaryl-(3')-chromenylium salts have previously not been known.

The object of the invention is to prepare previously unknown amino-substituted 2-cumaryl-(3')-chromenylium salts in an uncomplicated manner.

SUMMARY OF THE INVENTION

The task of the invention is to synthesize the previously unknown amino-substituted 2-cumaryl-(3')-chromenylium salts by using simply produced starting materials. The task is solved according to the invention by reacting substituted 3-acetylcumarines of type I ##STR2## in the presence of an acid HY with substituted salicylaldehydes of type II ##STR3## or by reacting 3-chloro-3-cumaryl-(3')-propene-(2)-iminium salts or -aldehydes of type III, respectively ##STR4## where X denotes an oxygen atom or an iminium salt group, in the presence of an acid HY with substituted phenols of type IV ##STR5## so that amino-substituted 2-cumaryl-(3')-chromenylium salts of Type V result, where R³ and/or R⁷ are a dialkyl or cycloalkyl- disubstituted amino group, hydrogen or a hydroxy group, and where R¹, R² and R⁴ as well as R⁵, R⁶ and R⁸ may be the same or different and are hydrogen, one alkoxy group or two of these substituents together form an aromatic ring and where Y⁻ is an acid radical as for instance C10₄ ⁻.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The invention will be explained infra by using the amino-substituted 2-cumaryl-(3')-chromenylium salts, listed in the appended tables as examples of execution which were prepared according to the following variations:

Variant A

0.01 Mol 3-acetyl curmarin of type I is mixed with 25 ml glacial acetic acid, 2 ml perchloric acid (70%) and 0.01 Mol substituted salicylaldehyde of type II. The mixture is heated 25 minutes to gentle boiling. The chromenylium compound of Type V precipitates on cooling, is suctioned off and recrystallized.

Variant B

The sequence is analogous to variant A except that 15 ml acetic anhydride are used instead of glacial acetic acid and the mixture is heated only 10 minutes to a gentle boil.

Variant C

0.01 Mol of acetylcumarin of type I and 0.01 Mol substituted salicylaldehyde of type II are dissolved in 20 ml 85% formic acid. Thereafter, hydrogen chloride is bubbled through for 5 hours at room temperature. After consecutively adding 100 ml glacial acetic acid and 30 ml 20% perchloric acid, the chromenylium compound of type V is precipitated by water, suctioned off and recrystallized.

Variant D

0.01 Mol 3-chloro-3-cumaryl-(3')-propene-(2)-iminium salt of type III (X=_(N) ⁺ (CH₃)₂ C10₄ ⁻), prepared according to WP C 07 D/209 424 and 0.01 Mol of a substituted phenol of type IV are suspended in 20 ml glacial acetic acid and heated under reflux for one hour. Thereafter, 2 ml 70% perchloric acid is carefully added, and the immediately occurring precipitate of the chromenylium compound of type V is suctioned and recrystallized.

Variant E

The sequence is analogous to variant D except that 15 ml acetone hydride is used and the mixture is heated only 10 minutes to boiling.

Variant F

The sequence is analogous to variant D but instead of using 3-chloro-3-cumaryl-(3')-propene-(2)-iminium salts, the 3-chloro-3-cumaryl-(3')-propene-(2)-aldehydes of type III (X=O) are used, prepared according to WP C07 D/209 424.

The examples of execution listed in the table are compounds which were recrystallized from glacial acetic acid. The melting points in all cases lie above 360° C.

    __________________________________________________________________________     Table showing prepared amino substituted 2-cumaryl-(3')-chromenylium           salts of type V (Y.sup.- ═ClO.sub.4)                                       Example                                  λmax                           of Execu-                                (lg ε)                                                                       yield in %                      tion No.                                                                            R.sup.1                                                                            R.sup.2                                                                            R.sup.3                                                                              R.sup.4                                                                           R.sup.5                                                                            R.sup.6                                                                            R.sup.7                                                                              R.sup.8                                                                             acetonitrile                                                                         of theory/variant               __________________________________________________________________________     1    --H --H --H   --H                                                                               --H --H N--Pyroli-                                                                           --H  563   86/A                                                          dinyl-     (4.41)                                                                               57/D                            2    (--CH═CH--).sub.2                                                                  --H   --H                                                                               --H --H N--Pyroli-                                                                           --H  582   91/A                                                          dinyl-     (4.39)                                                                               77/F                            3    --H --H N--Pyroli-                                                                           --H                                                                               --H --H --H   --H  639   81/A                                         dinyl-                      (4.78)                                4    --H --H N--Pyroli-                                                                           --H                                                                               --(CH═CH)--.sub.2                                                                  --H   --H  634   94/A                                         dinyl-                      (4.91)                                                                               78/E                            5    --H --H N--Pyroli-                                                                           --H                                                                               --H --H --H   --OCH.sub.3                                                                         613   94/A                                         dinyl-                      (4.52)                                6    --H --H --N(CH.sub.3).sub.2                                                                  --H                                                                               --H --H --H   --OCH.sub.3                                                                         605   98/A                                                                     (4.51)                                7    --H --H N--Pyroli-                                                                           --H                                                                               --H --H --OH  --H  610   91/A                                         dinyl-                      (4.94)                                8    --H --H --N(CH.sub.3).sub.2                                                                  --H                                                                               --H --H --N(CH.sub.3).sub.2                                                                  --H  650   89/A                                                                     (4.86)                                                                               87/B                            9    --H --H --N(C.sub.2 H.sub.5).sub.2                                                           --H                                                                               --H --H --N(C.sub.2 H.sub.5).sub.2                                                           --H  658   83/A                                                                     (4.95)                                                                               71/C                            10   --H --H N--Pyroli-                                                                           --H                                                                               --H --H N--Pyroli-                                                                           --H  659   92/A                                         dinyl-           dinyl-     (4.89)                                __________________________________________________________________________ 

We claim:
 1. Amino-substituted 2-cumaryl-3'-chromenylium salt of the formula ##STR6## wherein R³ and R⁷ are a dialkyl or cycloalkyl disubstituted amino group, hydrogen, or hydroxy group, provided that at least one of R³ and R⁷ is an amino group, R¹, R², R⁴, R⁵, R⁶, and R⁸ are hydrogen, an alkoxy group, or two of these substituents together form an aromatic ring, provided that R¹, R² and R⁴ may be the same or different, and R⁵, R⁶ and R⁸ may be the same or different, and Y⁻ is an acidic anion.
 2. The amino-substituted 2-cumaryl-3'-chromenylium salt of claim 1 wherein R¹ -R⁶ and R⁸ are hydrogen and R⁷ is N-pyrolidinyl-.
 3. The amino-substituted 2-cumaryl-3'-chromenylium salt of claim 1 wherein R¹ and R² together form (--CH═CH--)₂, R³ -R⁶ and R⁸ are hydrogen, and R⁷ is N-pyrolidinyl-.
 4. The amino-substituted 2-cumaryl-3'-chromenylium salt of claim 1 wherein R¹, R² and R⁴ -R⁸ are hydrogen, and R³ is N-pyrolidinyl-.
 5. The amino-substituted 2-cumaryl-3'-chromenylium salt of claim 1 wherein R¹, R², R⁴, R⁷ and R⁸ are hydrogen, R³ is N-pyrolidinyl-, and R⁵ and R⁶ together form (--CH═CH--)₂.
 6. The amino-substituted 2-cumaryl-3'-chromenylium salt of claim 1 wherein R¹, R², and R⁴ -R⁷ are hydrogen, R³ is N-pyrolidinyl-, and R⁸ is --OCH₃.
 7. The amino-substituted 2-cumaryl-3'-chromenylium salt of claim 1 wherein R¹, R², and R⁴ -R⁷ are hydrogen, R³ is --N(CH₃)₂, and R⁸ is --OCH₃.
 8. The amino-substituted 2-cumaryl-3'-chromenylium salt of claim 1 wherein R¹, R², R⁴ -R⁶, and R⁸ are hydrogen, R³ is N-pyrolidinyl-, and R⁷ is --OH.
 9. The amino-substituted 2-cumaryl-3'-chromenylium salt of claim 1 wherein R¹, R², R⁴ -R⁶, and R⁸ are hydrogen, and R³ and R⁷ are --N(CH₃)₂.
 10. The amino-substituted 2-cumaryl-3'-chromenylium salt of claim 1 wherein R¹, R², R⁴ -R⁶, and R⁸ are hydrogen, and R³ and R⁷ are --N(C₂ H₅)₂.
 11. The amino-substituted 2-cumaryl-3'-chromenylium salt of claim 1 wherein R¹, R², R⁴ -R⁶, and R⁸ are hydrogen and R³ and R⁷ are N-pyrolidinyl-. 